CN107429082B - Composition for forming cured film, alignment material, and phase difference material - Google Patents

Composition for forming cured film, alignment material, and phase difference material Download PDF

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CN107429082B
CN107429082B CN201680015301.9A CN201680015301A CN107429082B CN 107429082 B CN107429082 B CN 107429082B CN 201680015301 A CN201680015301 A CN 201680015301A CN 107429082 B CN107429082 B CN 107429082B
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group
component
cured film
compound
composition
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CN107429082A (en
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伊藤润
菅野裕太
畑中真
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Nissan Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
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    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
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    • C08G59/14—Polycondensates modified by chemical after-treatment
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    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
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    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
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    • C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
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    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
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    • C09D187/00—Coating compositions based on unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
    • C09D187/005—Block or graft polymers not provided for in groups C09D101/00 - C09D185/04
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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    • C09D7/63—Additives non-macromolecular organic
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3016—Polarising elements involving passive liquid crystal elements
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/13363—Birefringent elements, e.g. for optical compensation
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
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    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
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    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
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Abstract

The invention provides a composition for forming a cured film, which can form a cured film having excellent liquid crystal orientation and light transmittance when used as an orientation material and a polymerizable liquid crystal layer is arranged on the composition. The present invention provides a compound containing (A) a reaction product of a cinnamic acid compound represented by the following formula (1) and a compound having 1 or more epoxy groups in one molecule (wherein R is R) 1 、R 2 、R 3 、R 4 And R 5 Each independently represents a substituent selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms, a cyano group and a nitro group. ) And (B) a crosslinking agent, and an alignment material and a retardation material obtained by using the composition.

Description

Composition for forming cured film, alignment material, and phase difference material
Technical Field
The present invention relates to a composition for forming a cured film, an alignment material, and a retardation material.
Background
In recent years, in the field of displays for televisions and the like using liquid crystal panels, 3D displays capable of enjoying 3D images have been developed as a measure for improving performance. The 3D display can display an image having a stereoscopic effect by, for example, allowing the right eye of an observer to recognize an image for the right eye and allowing the left eye of the observer to recognize an image for the left eye.
There are various types of 3D displays for displaying 3D images, and a lenticular lens system, a parallax barrier system, and the like are known as systems that do not require special glasses.
As one of the methods of a display for observing a 3D image by an observer wearing a pair of glasses, a circularly polarized glasses method is known (see, for example, patent document 1).
In a 3D display of the circular polarized glasses system, a phase difference material is generally disposed on a display element for forming an image such as a liquid crystal panel. The phase difference material has a plurality of 2 types of phase difference regions having different phase difference characteristics, and is regularly arranged to form a patterned phase difference material. In the following description, a retardation material patterned by arranging a plurality of retardation regions having different retardation characteristics is referred to as a patterned retardation material.
The patterned retardation material can be produced by optically patterning a retardation material composed of polymerizable liquid crystal as disclosed in patent document 2, for example. Optical patterning of a phase difference material composed of polymerizable liquid crystal utilizes a photo-alignment technique known in the formation of an alignment material for a liquid crystal panel. That is, a coating film made of a photo-alignment material is provided on a substrate, and 2 types of polarized light having different polarization directions are irradiated thereto. Then, a photo-alignment film was obtained as an alignment material in which 2 types of liquid crystal alignment regions having different liquid crystal alignment control directions were formed. The photo-alignment film is coated with a phase difference material in a solution state containing a polymerizable liquid crystal to align the polymerizable liquid crystal. Then, the aligned polymerizable liquid crystal is cured to form a patterned retardation material.
In the formation of alignment materials using a photo-alignment technique of a liquid crystal panel, as a material having photo-alignment properties that can be used, an acrylic resin or a polyimide resin having a photo-dimerization site such as a cinnamoyl group or a chalcone group in a side chain thereof is known. It has been reported that these resins exhibit a property capable of controlling the alignment of liquid crystals by polarized UV irradiation (hereinafter, also referred to as liquid crystal alignment property) (see patent documents 3 to 5).
Documents of the prior art
Patent document
Patent document 1 Japanese patent laid-open publication No. H10-232365
Patent document 2 Japanese patent laid-open No. 2005-49865
Patent document 3 specification of Japanese patent No. 3611342
Patent document 4 Japanese patent laid-open publication No. 2009-058584
Patent document 5 Japanese patent application laid-open No. 2001-517719
Disclosure of Invention
Problems to be solved by the invention
As described above, the patterned retardation material is configured by laminating a cured polymerizable liquid crystal layer on a photo alignment film as an alignment material. Also, the patterned phase difference material having such a stacked structure may be directly used for the construction of a 3D display in the stacked state.
Therefore, it is necessary to develop a cured film that can be used as an alignment material having both excellent liquid crystal alignment properties and light transmission properties, and a cured film-forming composition for forming the cured film.
The object of the present invention is achieved based on the above knowledge and research results. That is, an object of the present invention is to provide a composition for forming a cured film, which is suitable for forming a cured film having excellent liquid crystal alignment properties and light transmission properties. In particular, an object of the present invention is to provide a composition for forming a cured film which can form a cured film that exhibits excellent liquid crystal alignment properties and light transmittance when used as an alignment material and a polymerizable liquid crystal layer is disposed thereon.
The purpose of the present invention is to provide an alignment material having excellent liquid crystal alignment properties and light transmission characteristics.
The purpose of the present invention is to provide a phase difference material capable of performing optical patterning with high accuracy.
Other objects and advantages of the present invention will become apparent from the following description.
Means for solving the problems
The present inventors have conducted intensive studies in order to achieve the above object and, as a result, have found that a cured film having excellent orientation can be formed regardless of the kind of a base material by selecting a cured film-forming material based on a compound obtained by reacting a specific cinnamic acid compound and a compound having 1 or more epoxy groups in one molecule as the component (a), thereby completing the present invention.
That is, the aspect 1 of the present invention relates to a composition for forming a cured film, which comprises a compound as the component (A) and a crosslinking agent as the component (B),
the compound as the component (A) is a reaction product of a cinnamic acid compound represented by the following formula (1) and a compound having 1 or more epoxy groups in one molecule,
Figure BDA0001405366870000031
in the formula, R 1 、R 2 、R 3 、R 4 And R 5 Each independently represents a hydrogen atom, a halogen atom, C 1 ～C 6 Alkyl radical, C 1 ～C 6 Haloalkyl, C 1 ～C 6 Alkoxy radical, C 1 ～C 6 Haloalkoxy, C 3 ～C 8 Cycloalkyl radical, C 3 ～C 8 Halogenocycloalkyl, C 2 ～C 6 Alkenyl radical, C 2 ～C 6 Haloalkenyl, C 3 ～C 8 Cycloalkenyl radical, C 3 ～C 8 Halogenated cycloalkenyl radical, C 2 ～C 6 Alkynyl, C 2 ～C 6 Halogenated alkynyl, C 1 ～C 6 Alkoxy radical, C 1 ～C 6 Haloalkoxy, (C) 1 ～C 6 Alkyl) carbonyl, (C) 1 ～C 6 Haloalkyl) carbonyl, (C) 1 ～C 6 Alkoxy) carbonyl (C) 1 ～C 6 Haloalkoxy) carbonyl, (C) 1 ～C 6 Alkylamino) carbonyl group, (C) 1 ～C 6 Haloalkyl) aminocarbonyl, di (C) 1 ～C 6 Alkyl) aminocarbonyl, cyano and nitro.
In view 2 of the present invention, the cured film forming composition according to view 1, wherein the crosslinking agent as the component (B) is a crosslinking agent having a methylol group or an alkoxymethyl group.
An aspect 3 of the present invention relates to the cured film-forming composition according to aspect 1 or 2, further comprising a polymer having a thermally crosslinkable group as the component (C).
Aspect 4 of the present invention relates to the composition for forming a cured film according to any one of aspects 1 to 3, further comprising a crosslinking catalyst as the component (D).
The composition for forming a cured film according to aspect 5 of the present invention is the composition for forming a cured film according to any one of aspects 1 to 4, which contains the component (B) in an amount of 1 to 600 parts by mass based on 100 parts by mass of the component (a).
The present invention, in view 6, relates to the cured film forming composition according to any one of views 3 to 5, which comprises 100 parts by mass of the total amount of the component (a) and the crosslinking agent as the component (B), and 1 to 400 parts by mass of the component (C).
The composition for forming a cured film according to aspect 7 of the present invention relates to any one of aspects 4 to 6, wherein the component (D) is contained in an amount of 0.01 to 20 parts by mass based on 100 parts by mass of the total amount of the component (a) and the crosslinking agent as the component (B).
An aspect 8 of the present invention relates to a cured film, which is a cured product of the composition for forming a cured film according to any one of aspects 1 to 7.
An aspect 9 of the present invention relates to an alignment material, which is a cured product of the composition for forming a cured film according to any one of aspects 1 to 7.
An aspect 10 of the present invention relates to a retardation material produced using a cured film obtained from the composition for forming a cured film according to any one of aspects 1 to 7.
Effects of the invention
The present invention can provide a cured film having excellent liquid crystal alignment properties and light transmittance, and a composition for forming a cured film suitable for forming the cured film.
The present invention can provide an alignment material having excellent liquid crystal alignment properties and light transmittance.
The present invention can provide a phase difference material capable of high-precision optical patterning.
Detailed Description
< composition for Forming cured film >
The composition for forming a cured film of the present invention contains a compound as component (a) which is a reaction product of a specific cinnamic acid compound and a compound having 1 or more epoxy groups in one molecule, and a crosslinking agent as component (B). The composition for forming a cured film of the present invention may further contain a polymer having a thermally crosslinkable group as the component (C) in addition to the components (a) and (B). Further, a crosslinking catalyst may be contained as the component (D). Further, a component (E) that improves the adhesiveness of the formed cured film (hereinafter, also referred to as adhesion improving component) may be contained. The solvent and other additives may be contained within the range not to impair the effects of the present invention.
Hereinafter, the details of each component will be described.
< component (A) >
The component (a) contained in the cured film-forming composition of the present invention is a compound obtained by reacting a cinnamic acid compound represented by the following formula (1) with a compound having 1 or more epoxy groups in one molecule.
Figure BDA0001405366870000051
(wherein R is 1 、R 2 、R 3 、R 4 And R 5 Each independently represents a hydrogen atom, a halogen atom, C 1 ～C 6 Alkyl radical, C 1 ～C 6 Haloalkyl, C 1 ～C 6 Alkoxy radical, C 1 ～C 6 Haloalkoxy, C 3 ～C 8 Cycloalkyl radical, C 3 ～C 8 Halogenocycloalkyl, C 2 ～C 6 Alkenyl radical, C 2 ～C 6 Haloalkenyl, C 3 ～C 8 Cycloalkenyl radical, C 3 ～C 8 Halogenated cycloalkenyl radical, C 2 ～C 6 Alkynyl, C 2 ～C 6 Halogenated alkynyl, C 1 ～C 6 Alkoxy radical, C 1 ～C 6 Haloalkoxy, (C) 1 ～C 6 Alkyl) carbonyl (C) 1 ～C 6 Haloalkyl) carbonyl, (C) 1 ～C 6 Alkoxy) carbonyl (C) 1 ～C 6 Haloalkoxy) carbonyl, (C) 1 ～C 6 Alkylamino) carbonyl group, (C) 1 ～C 6 Haloalkyl) aminocarbonyl, di (C) 1 ～C 6 Alkyl) aminocarbonyl, cyano and substituents in the nitro group. )
Examples of the halogen atom in the present specification include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. In the present specification, the term "halogen" also means these halogen atoms.
In this specification, "C a ～C b The term "alkyl" denotes a linear or branched hydrocarbon group having a to b carbon atoms, and specific examples thereof include methyl, ethyl, n-propyl and isopropylN-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl, 1-dimethylpropyl, 1, 2-dimethylpropyl, 2-dimethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 1-dimethylbutyl, 1, 3-dimethylbutyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and the like, selected within the specified number of carbon atoms.
In this specification, "C a ～C b The term "haloalkyl group" means a linear or branched hydrocarbon group having a to b carbon atoms, in which a hydrogen atom bonded to a carbon atom is optionally substituted with a halogen atom, and when substituted with 2 or more halogen atoms, these halogen atoms may be the same or different. <xnotran> , , , , , , , , , , , , , , ,2- ,2- ,2- ,2,2- ,2- -2- ,2,2- ,2- -2- ,2,2,2- ,2- -2,2- ,2,2- -2- ,2,2,2- ,2- -2,2- ,2- -2- -2- ,2- -2,2- ,1,1,2,2- , ,1- -1,2,2,2- ,2- -1,1,2,2- ,1,2- -1,2,2- ,2- -1,1,2,2- ,2- ,2- ,2- ,2- -2- ,2,3- ,2- -3- ,3- -2- ,2,3- ,3,3,3- ,3- -3,3- ,2,2,3,3- ,2- -3,3,3- ,2,2,3,3,3- ,1,1,2,3,3,3- , </xnotran> Heptafluoropropyl, 2, 3-dichloro-1, 2, 3-pentafluoropropyl, 2-fluoro-1-methylethyl 2-chloro-1-methylethyl, 2-bromo-1-methylethyl, 2-trifluoro-1- (trifluoromethyl) ethyl 1, 2-tetrafluoro-1- (trifluoromethyl) ethyl group, 2,3, 4-hexafluorobutyl group, and 2,2,3,4,4,4-hexafluorobutyl, 2,2,3,3,4,4,4-heptafluorobutyl, 1,1,2,2,3,3,4,4-octafluorobutyl,Nonafluorobutyl, 4-chloro-1, 2,3, 4-octafluorobutyl, 2-fluoro-2-methylpropyl, 2-chloro-1, 1-dimethylethyl 2-bromo-1, 1-dimethylethyl, 5-chloro-2, 3,4, 5-heptafluoropentyl, tridecafluorohexyl, and the like, selected within the respective specified carbon number ranges.
In this specification, "C a ～C b The term "cycloalkyl group" means a cyclic hydrocarbon group having a to b carbon atoms and can form a3 to 6-membered ring having a monocyclic or complex ring structure. In addition, each ring may be optionally substituted with an alkyl group within a specified range of the number of carbon atoms. Specific examples thereof include cyclopropyl, 1-methylcyclopropyl, 2-dimethylcyclopropyl, 2, 3-tetramethylcyclopropyl, cyclobutyl, cyclopentyl, 2-methylcyclopentyl, 3-methylcyclopentyl, cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, bicyclo [2.2.1 ] bicyclo]Heptane-2-yl group, etc., selected within the respective specified carbon number ranges.
In this specification, "C a ～C b The term "halocycloalkyl group" means a cyclic hydrocarbon group having a to b carbon atoms, wherein hydrogen atoms bonded to carbon atoms are optionally substituted with halogen atoms, and can have a monocyclic or complex ring structure having 3 to 6-membered rings. In addition, each ring may be optionally substituted with an alkyl group within a predetermined range of the number of carbon atoms, and the halogen atom may be substituted with either a cyclic moiety or a side chain moiety, or both, and when substituted with 2 or more halogen atoms, these halogen atoms may be the same or different. Specific examples thereof include 2, 2-difluorocyclopropyl group, 2-dichlorocyclopropyl group, 2-dibromocyclopropyl group, 2-difluoro-1-methylcyclopropyl group, 2-dichloro-1-methylcyclopropyl group 2, 2-dibromo-1-methylcyclopropyl group, 2, 3-tetrafluorocyclobutyl group, 2- (trifluoromethyl) cyclohexyl group, 3- (trifluoromethyl) cyclohexyl group, 4- (trifluoromethyl) cyclohexyl group and the like, selected within the respective specified carbon number ranges.
In this specification, "C a ～C b The term "alkenyl group" means a linear or branched unsaturated hydrocarbon group having a to b carbon atoms and having 1 or 2 or more double bonds in the molecule, and specific examples thereof includeFor example, vinyl, 1-propenyl, 2-propenyl, 1-methylvinyl, 2-butenyl, 1-methyl-2-propenyl, 2-pentenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 2-ethyl-2-propenyl, 1-dimethyl-2-propenyl, 2-hexenyl, 2-methyl-2-pentenyl, 2, 4-dimethyl-2, 6-heptadienyl, 3, 7-dimethyl-2, 6-octadienyl and the like, selected within the respective specified carbon number ranges.
In this specification, "C a ～C b The term "haloalkenyl group" means a linear or branched unsaturated hydrocarbon group having a to b carbon atoms, in which a hydrogen atom bonded to a carbon atom is optionally substituted with a halogen atom, and which has 1 or 2 or more double bonds in the molecule. When substituted with 2 or more halogen atoms, these halogen atoms may be the same or different. Specific examples thereof include, for example, 2-dichlorovinyl, 2-fluoro-2-propenyl, 2-chloro-2-propenyl, 3-chloro-2-propenyl, 2-bromo-2-propenyl, 3-difluoro-2-propenyl, 2, 3-dichloro-2-propenyl, 3-dichloro-2-propenyl, 2, 3-dibromo-2-propenyl 2,3,3-trifluoro-2-propenyl group, 2,3,3-trichloro-2-propenyl group, 1- (trifluoromethyl) ethenyl group, 3-chloro-2-butenyl group, 3-bromo-2-butenyl group, 4-difluoro-3-butenyl group, 3, 4-trifluoro-3-butenyl group, 3-chloro-4,4, 4-trifluoro-2-butenyl group, 3-bromo-2-methyl-2-propenyl group and the like, selected within the respective specified carbon number ranges.
In this specification, "C a ～C b The term "cycloalkenyl group" refers to an unsaturated hydrocarbon group having 1 or 2 or more double bonds and having a cyclic structure of a to b carbon atoms, and may have a monocyclic or complex ring structure having 3 to 6 membered rings. Further, each ring may be optionally substituted with an alkyl group within the specified carbon number range, and the double bond may be in any form of endo-or exo-. Specific examples thereof include 2-cyclopenten-1-yl, 3-cyclopenten-1-yl, 2-cyclohexen-1-yl, 3-cyclohexen-1-yl, bicyclo [2.2.1 ] bi]-5-hepten-2-yl, etc., selected within the respective specified carbon number ranges.
In this specification, "C a ～C b The term "halocycloalkenyl" denotes a group bonded to a carbon atomAn unsaturated hydrocarbon group having a cyclic structure of a to b carbon atoms optionally substituted with a halogen atom and having 1 or 2 or more double bonds, and having a3 to 6-membered ring in a monocyclic or composite ring structure. Further, each ring may be optionally substituted with an alkyl group within the specified number of carbon atoms, and the double bond may be in any form of endo-or exo-. The halogen atom may be substituted with 2 or more halogen atoms, and these halogen atoms may be the same or different from each other. Specific examples thereof include 2-chlorobicyclo [ 2.2.1%]-5-hepten-2-yl, etc., selected within the respective specified carbon number ranges.
In this specification, "C a ～C b The term "alkynyl group" means an unsaturated hydrocarbon group which is linear or branched and has 1 or 2 or more acetylene bonds in the molecule and has a carbon number of a to b, and specific examples thereof include ethynyl, 1-propynyl, 2-butynyl, 1-methyl-2-propynyl, 2-pentynyl, 1-methyl-2-butynyl, 1-dimethyl-2-propynyl and 2-hexynyl, and these are selected from the specified carbon number ranges.
In this specification, "C a ～C b The term "haloalkynyl group" refers to a linear or branched unsaturated hydrocarbon group having 1 or 2 or more acetylene bonds in the molecule, in which a hydrogen atom bonded to a carbon atom is optionally substituted with a halogen atom and which has a carbon number of a to b. In this case, when substituted with 2 or more halogen atoms, these halogen atoms may be the same or different from each other. Specific examples thereof include 2-chloroethynyl, 2-bromoethynyl, 2-iodoethynyl, 3-chloro-2-propynyl, 3-bromo-2-propynyl, 3-iodo-2-propynyl and the like, and these are selected within the respective specified carbon number ranges.
In this specification, "C a ～C b The term "alkoxy" denotes an alkyl-O-group having a carbon number of a to b and having the aforementioned meaning, and specific examples thereof include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-butoxyPentyloxy group, n-hexyloxy group, etc., selected within the respective specified carbon number ranges.
In this specification, "C a ～C b <xnotran> " , a ～ b -O- , , , , ,2- ,2- ,2,2,2- ,1,1,2,2, - ,2- -1,1,2- ,2- -1,1,2- , ,2,2- -1,1,2- ,2,2,2- -1,1- ,2- -1,1,2,2- ,2,2,3,3- ,1,1,2,3,3,3- ,2,2,2- -1- ( ) , ,2- -1,1,2,3,3,3- , . </xnotran>
In this specification, "(C) a ～C b Alkyl) carbonyl "means an alkyl-C (O) -group having a carbon number of a to b and having the aforementioned meaning, and specific examples thereof include acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, 2-methylbutyryl, pivaloyl, hexanoyl, heptanoyl and the like, and are selected from the specified carbon number ranges.
In this specification, "(C) a ～C b Haloalkyl) carbonyl "means a haloalkyl-C (O) -group having a carbon number of a to b as defined above, and specific examples thereof include fluoroacetyl, chloroacetyl, difluoroacetyl, dichloroacetyl, trifluoroacetyl, chlorodifluoroacetyl, bromodifluoroacetyl, trichloroacetyl, pentafluoropropionyl, heptafluorobutyryl, 3-chloro-2, 2-dimethylpropionyl, and the like, and are selected from the specified carbon number ranges.
In this specification, "(C) a ～C b Alkoxy) carbonyl "means an alkyl-O-C (O) -group having the aforementioned meaning and having a to b carbon atoms, and specific examples thereof include methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonylAnd tert-butoxycarbonyl group, etc., selected within the respective specified carbon number ranges.
In this specification, "(C) a ～C b Haloalkoxy) carbonyl "means a haloalkyl-O-C (O) -group having the aforementioned meaning having a to b carbon atoms, specific examples thereof include, for example, 2-chloroethoxycarbonyl group, 2-difluoroethoxycarbonyl group, 2-trifluoroethoxycarbonyl group, 2-trichloroethoxycarbonyl group and the like, and are selected from the specified ranges of the number of carbon atoms.
In this specification, "(C) a ～C b The term "alkylamino) carbonyl" refers to a carbamoyl group in which one of the hydrogen atoms is substituted with an alkyl group having a to b carbon atoms as defined above, and specific examples thereof include methylcarbamoyl, ethylcarbamoyl, n-propylcarbamoyl, isopropylcarbamoyl, n-butylcarbamoyl, isobutylcarbamoyl, sec-butylcarbamoyl and tert-butylcarbamoyl groups, and these groups are selected from the specified ranges of the number of carbon atoms.
In this specification, "(C) a ～C b The term "haloalkylamino) carbonyl" denotes a carbamoyl group wherein one of the hydrogen atoms is substituted by a haloalkyl group having the aforementioned meaning having a to b carbon atoms, and specific examples thereof include 2-fluoroethylcarbamoyl, 2-chloroethylcarbamoyl, 2-difluoroethylcarbamoyl and 2, 2-trifluoroethylcarbamoyl, which are selected from the specified carbon number ranges.
In this specification, "two (C) a ～C b Alkyl) aminocarbonyl "represents a carbamoyl group in which both hydrogen atoms are substituted with an alkyl group having the aforementioned meaning of having a to b carbon atoms, which may be the same or different, and specific examples thereof include N, N-dimethylcarbamoyl group, N-ethyl-N-methylcarbamoyl group, N-diethylcarbamoyl group, N-di-N-propylcarbamoyl group, N-di-N-butylcarbamoyl group, and the like, and are selected from the specified carbon number ranges.
A substituent R of a cinnamic acid compound represented by the formula (1) 1 、R 2 、R 3 、R 4 And R 5 Particularly preferably, each independently is selected from the group consisting of a hydrogen atom, a halogen atom, C 1 ～C 6 Alkyl radical, C 1 ～C 6 Haloalkyl, C 1 ～C 6 Alkoxy radical, C 1 ～C 6 Haloalkoxy, cyano and nitro.
Further, as R 3 The substituent other than the hydrogen atom in the above definition is preferably selected from a halogen atom and C in view of orientation sensitivity, and more preferably 1 ～C 6 Alkyl radical, C 1 ～C 6 Haloalkyl, C 1 ～C 6 Alkoxy radical, C 1 ～C 6 Haloalkoxy, cyano and nitro.
Examples of the compound having 1 or more epoxy groups in one molecule include compounds having a molecular weight of 100 to 5000.
The monoepoxy compound of the compound having 1 or more epoxy groups in one molecule is not particularly limited, and examples thereof include butyl glycidyl ether, hexyl glycidyl ether, phenyl glycidyl ether, p-xylyl glycidyl ether, allyl glycidyl ether, p-tert-butylphenyl glycidyl ether, ethylene oxide, propylene oxide, cyclopentane oxide, butylene oxide, epichlorohydrin, propylene oxide, glycidyl alcohol (i.e., ethylene oxide carbinol), glycidyl acetate, glycidyl butyrate, glycidyl hexanoate, glycidyl benzoate, tetrahydropyran, cyclopentane oxide, and cyclohexane oxide.
Among compounds having 1 or more epoxy groups in one molecule, examples of the epoxy compound having 2 or more epoxy groups include tris (2, 3-epoxypropyl) isocyanurate, 1, 4-butanediol diglycidyl ether, 1, 2-epoxy-4- (epoxyethyl) cyclohexane, glycerol triglycidyl ether, diethylene glycol diglycidyl ether, 2, 6-diglycidyl phenyl glycidyl ether, 1, 3-tris [ p- (2, 3-epoxypropoxy) phenyl ] propane, 1, 2-cyclohexanedicarboxylic acid diglycidyl ester, 4' -methylenebis (N, N-diglycidylaniline), 3, 4-epoxycyclohexanecarboxylic acid 3, 4-cyclohexylmethyl ester, trimethylolethane triglycidyl ether, bisphenol-a-diglycidyl ether, and pentaerythritol polyglycidyl ether.
Further, a commercially available compound can be used from the viewpoint of easy availability. Specific examples (trade names) thereof are listed below, but not limited thereto: epoxy resins having an amino group such as YH-434 and YH434L (manufactured by Doudou Kabushiki Kaisha Co., ltd.); \\ 12456091254012512512512512512509125125125125091251251251254089, GT 125124125125891251251251251251250912512512589, 12556125125091251254089; \\ 12456091254012589gt, GT-302, 12475\\ 124125124891; \\ 1247512461\\ 12469124124124124124124893000 (manufactured by chemical industries (ltv.l.124) 1247512423; bisphenol a epoxy resins such as jER (registered trademark) 1001, jER 1002, jER 1003, jER 1004, jER 1007, and jER 828 (manufactured by mitsubishi chemical corporation); \\ 12456671254088807 (oleo 1247112455\\ 124611250971 (strain 125725; \\ 1249712509125092471 (manufactured by 125721252450); <xnotran> デナコール EX-252 (ナガセケムテックス () ), CY175, CY177, CY179, アラルダイト CY-182, アラルダイト CY-192, アラルダイト CY-184 ( CIBA-GEIGYA.G ), エピクロン 200, エピクロン 400 ( インキ () ( DIC ()) ), jER ( ) 871, jER 872 ( ジャパンエポキシレジン () ), ED-5661, ED-5662 ( セラニーズコーティング () ) ; </xnotran> 1258767124671254090, 125124674090, 1251248767125, 125674090, 124871248767125, 1248712467125, 1256712567411, 124124124124124124124124125, 125671241251248790, 1251241256712412512412587125, 124125124125124678712512487125, 125124125124678712512487125, 125124125124125124678712512412587102.
The compound having 1 or more epoxy groups in one molecule is preferably a compound having 2 or more epoxy groups in the molecule in view of forming a crosslink.
When the cinnamic acid compound represented by the formula (1) is reacted with the epoxy compound to obtain the compound as the component (a), it is preferable to react the cinnamic acid compound represented by the formula (1) in an organic solvent at room temperature in an amount of 1 to 1.2 equivalents relative to the epoxy group of the epoxy compound. Examples of the organic solvent in this case include those described in < solvent > described below.
The compound having 1 or more epoxy groups in one molecule used as the component (a) in the present invention may be a mixture of a plurality of such compounds.
< ingredient (B) >
The component (B) in the composition for forming a cured film of the present invention is a crosslinking agent.
The crosslinking agent (B) component preferably has a group capable of crosslinking with the functional group capable of thermal crosslinking of the component (A), for example, a methylol group or an alkoxymethyl group.
Examples of the compound having such a group include methylol compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, and alkoxymethylated melamine.
The thermally crosslinkable functional group of the component (a) is mainly a hydroxyl group.
Specific examples of alkoxymethylated glycolurils include 1,3,4, 6-tetrakis (methoxymethyl) glycoluril, 1,3,4, 6-tetrakis (butoxymethyl) glycoluril, 1,3,4, 6-tetrakis (hydroxymethyl) glycoluril, 1, 3-bis (hydroxymethyl) urea, 1, 3-tetrakis (butoxymethyl) urea, 1, 3-tetrakis (methoxymethyl) urea, 1, 3-bis (hydroxymethyl) -4, 5-dihydroxy-2-imidazolidinone, and 1, 3-bis (methoxymethyl) -4, 5-dimethoxy-2-imidazolidinone. Examples of commercially available products include japanese patent publication No. 12469124521248612412412463\124125801252240125; \12474 (old trilobi \12469\1245212486\12412483 (strain) \\12463; \\124693 (registered trademark), 125231255412480125125125401174 (registered trademark), a compound such as 1251251253163; UFR (registered trademark) 65), butylated urea resin (trade names: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11 HV), DIC (strain) (old japan: 125523161125 (glaciers) J-300S, 125051245912511255912511251, 1250512512505125125591251251, 125051250512512412559.
Specific examples of alkoxymethylated benzoguanamine include tetramethoxymethylbenzguanamine and the like. The patent is described in general formula (1) in the general formula (1) as a commercial product, in the general formulae (1) Nos. 2 (1) may be enumerated: 124691241245286124 (strain: 1241251247420 (198124) 12442), (12552124521243 (tradename 12412412412512512523124) and (11241255912412491) patent (tradename: 12412412512412512420, 21241241251245912420.
Specific examples of alkoxymethylated melamine include hexamethoxymethylmelamine and the like. As commercially available products, there are exemplified compounds of methoxy methyl melamine (trade name: 124696986, described in japanese patent publication No. 1245212486\\124631247312412588125125224074 (strain 1241246986; \\ 124523, \\ 12452125693 (registered trademark), 1255212512523301, 1245212512512512512523301, \\ 1245212513, 12512523303, 12552125125693; 125112467506 (registered trademark), 125121215991, MW-124124631249112420, 12412412412412412459, 112412412412420, 112412412412491, 1241241245912420.
Further, the compound may be one obtained by condensation of a melamine compound, a urea compound, a glycoluril compound, and a benzoguanamine compound, in which the hydrogen atom of the amino group is substituted with a hydroxymethyl group or an alkoxymethyl group. Examples of the high molecular weight compound include those produced from melamine compounds and benzoguanamine compounds described in U.S. Pat. No. 6323310. Examples of the commercially available products of the melamine compound include trade names: \124693, \\ 12513, \ 12523 (registered trademark) 303, and the like, and as commercial products of the aforementioned benzoguanamine compounds, trade names: \\ 124523 (registered trademark) 1123 (above: japanese patent No. 12469\1246312452124861241241241241258012412588 (strain 12412412412474 (strain 12412412412412452124).
Further, as the crosslinking agent of the component (B), a polymer produced using an acrylamide compound or a methacrylamide compound substituted with a methylol group (i.e., a methylol group) or an alkoxymethyl group, such as N-methylolacrylamide, N-methoxymethyl (methacrylamide), N-ethoxymethacrylamide, and N-butoxymethyl (methacrylamide) group, can be used.
Examples of such polymers include poly (N-butoxymethylacrylamide), a copolymer of N-butoxymethylacrylamide and styrene, a copolymer of N-methylolmethacrylamide and methyl methacrylate, a copolymer of N-ethoxymethylmethacrylamide and benzyl methacrylate, and a copolymer of N-butoxymethylacrylamide and benzyl methacrylate and 2-hydroxypropyl methacrylate. The weight average molecular weight (polystyrene equivalent) of such a polymer is 1,000 to 500,000, preferably 2,000 to 200,000, more preferably 3,000 to 150,000, and still more preferably 3,000 to 50,000.
These crosslinking agents may be used alone or in combination of 2 or more. Further, an example of the component (B) is a polymer having an N-alkoxymethyl group and a side chain group containing a polymerizable C = C double bond as a unit structure (hereinafter, also referred to as a specific copolymer 2).
Examples of the N, i.e., nitrogen atom of the N-alkoxymethyl group include a nitrogen atom of an amide, a nitrogen atom of a thioamide, a nitrogen atom of urea, a nitrogen atom of thiourea, a nitrogen atom of a carbamate, and a nitrogen atom bonded to the ortho-position of the nitrogen atom of the nitrogen-containing heterocycle. Thus, the N-alkoxymethyl group may have a structure in which an alkoxymethyl group is bonded to a nitrogen atom selected from the group consisting of an amide nitrogen atom, a thioamide nitrogen atom, a urea nitrogen atom, a thiourea nitrogen atom, a carbamate nitrogen atom, a nitrogen atom bonded to the ortho position of a nitrogen atom of a nitrogen-containing heterocyclic ring, and the like.
The specific copolymer 2 is imparted with an N-alkoxymethyl group, which can be achieved by using a monomer capable of imparting an N-alkoxymethyl group (hereinafter, also referred to as a specific monomer X1) at the time of polymerization.
The monomer capable of imparting an N-alkoxymethyl group is not particularly limited as long as it is a monomer having an N-alkoxymethyl group, and examples thereof include compounds represented by the following formula (X1).
Figure BDA0001405366870000141
(wherein R is 31 Represents a hydrogen atom or a methyl group, R 32 Represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms)
<xnotran> , , , , , , , , , , ,1- - ,2- - ,3- - ,1,1- - ,1,2- - ,2,2- - ,1- - , ,1- - ,2- - ,3- - ,4- - ,1,1- - ,1,2- - ,1,3- - ,2,2- - ,2,3- - ,3,3- - ,1- - ,2- - ,1,1,2- - ,1,2,2- - ,1- -1- - ,1- -2- - , ,1- - ,2- - ,3- - ,1,1- - ,1,2- - ,1,3- - ,2,2- - ,2,3- - ,3,3- - ,1- - , </xnotran> 2-ethyl-n-pentyl, 3-ethyl-n-pentyl, 1-methyl-1-ethyl-n-butyl, 1-methyl-2-ethyl-n-butyl, 1-ethyl-2-methyl-n-butyl, 2-methyl-2-ethyl-n-butyl, 2-ethyl-3-methyl-n-butyl, n-octyl, 1-methyl-n-heptyl, 2-methyl-n-heptyl, 3-methyl-n-heptyl, 1-dimethyl-n-hexyl, 1, 2-dimethyl-n-hexyl, 1, 3-dimethyl-n-hexyl, 2-dimethyl-n-hexyl, 2, 3-dimethyl-n-hexyl, 3-dimethyl-n-hexyl, 1-ethyl-n-hexyl, 2-ethyl-n-hexyl, 3-ethyl-n-hexyl, 1-methyl-1-ethyl-n-pentyl, 1-methyl-2-ethyl-n-pentyl, 1-methyl-3-ethyl-n-pentyl, 2-methyl-2-ethyl-n-pentyl, 2-methyl-3-ethyl-n-pentyl, 3-methyl-n-pentyl, 3-ethyl-n-nonyl, n-decyl and the like.
Specific examples of the compound represented by the formula (X1) include acrylamide compounds or methacrylamide compounds substituted with a methylol group or an alkoxymethyl group, such as N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, and N-butoxymethyl (meth) acrylamide. The term "(meth) acrylamide" refers to both methacrylamide and acrylamide.
Examples of the side chain group containing a polymerizable C = C double bond include an acryloyl group, a methacryloyl group, a vinyl group, an allyl group, and a maleimide group.
Examples of the side chain group containing a polymerizable C = C double bond include organic groups having 3 to 16 carbon atoms and having a polymerizable C = C double bond at the end, and a side chain group represented by formula (b 2) is particularly preferable. The side chain group represented by the formula (b 2) is bonded to the ester moiety of the acrylic polymer as shown in the formula (b 2-1).
Figure BDA0001405366870000161
R in the formula (b 2) 41 The (b) has 1 to 14 carbon atoms and is an organic group selected from an aliphatic group, an aliphatic group having a cyclic structure and an aromatic group, or an organic group obtained by combining a plurality of organic groups in the group. R is 41 It may contain an ester group, an ether group, an amide group, a urethane group or the like.
In the formula (b 2), R is preferred 42 Is a hydrogen atom or a methyl group, R 42 The side chain group in the case of a hydrogen atom is more preferably a side chain group having an acryloyl group, a methacryloyl group or a styryl group at the end.
In the formula (b 2-1), R 43 Is a hydrogen atom or a methyl group.
The method for obtaining the polymer having the side chain group is not particularly limited. For example, an acrylic polymer having a specific functional group is produced in advance by a polymerization method such as radical polymerization. Next, the specific functional group is reacted with a compound having a polymerizable C = C double bond at the end and a functional group capable of reacting with the specific functional group to form a chemical bond (hereinafter, referred to as a specific compound) to form a side chain group, whereby the side chain group containing a polymerizable C = C double bond is introduced into the specific copolymer 2.
The specific functional group herein means a functional group such as a carboxyl group, a glycidyl group, a hydroxyl group, an amino group having an active hydrogen, a phenolic hydroxyl group or an isocyanate group, or a plurality of functional groups selected from these.
In the reaction for forming the side chain group, a preferable combination of the specific functional group and a functional group capable of reacting with the specific functional group of the specific compound to form a chemical bond is: carboxyl and epoxy groups, hydroxyl and isocyanate groups, phenolic hydroxyl and epoxy groups, carboxyl and isocyanate groups, amino and isocyanate groups, or hydroxyl and acid chloride, and the like. Still more preferably, the combination is carboxyl and glycidyl methacrylate, or hydroxyl and isocyanatoethyl methacrylate.
In the reaction for forming the side chain group, the polymer having a specific functional group is preferably a copolymer obtained by polymerizing a monomer capable of providing an N-alkoxymethyl group (i.e., the specific monomer X1) and a monomer having a specific functional group, i.e., a monomer having a carboxyl group, a glycidyl group, a hydroxyl group, an active hydrogen-containing amino group, a phenolic hydroxyl group, an isocyanate group or the like (hereinafter, also referred to as the specific monomer X3), and the number average molecular weight thereof is preferably 2,000 to 25,000. The monomer having a specific functional group used in the polymerization may be used alone, or a plurality of monomers may be used in combination if they are not reacted during the polymerization.
Specific examples of the monomer used for obtaining a polymer having a specific functional group, that is, the specific monomer X3, are listed below. But is not limited to these.
Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono- (2- (acryloyloxy) ethyl) phthalate, mono- (2- (methacryloyloxy) ethyl) phthalate, N- (carboxyphenyl) maleimide, N- (carboxyphenyl) methacrylamide, and N- (carboxyphenyl) acrylamide.
Examples of the monomer having a glycidyl group include glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, 3-vinyl-7-oxabicyclo [4.1.0] heptane, 1, 2-epoxy-5-hexene, and 1, 7-octadiene monoepoxide.
Examples of the monomer having a hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2, 3-dihydroxypropyl acrylate, 2, 3-dihydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, caprolactone 2- (acryloyloxy) ethyl ester, caprolactone 2- (methacryloyloxy) ethyl ester, poly (ethylene glycol) ethyl ether acrylate, poly (ethylene glycol) ethyl ether methacrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic acid-6-lactone, and 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic acid-6-lactone.
Examples of the monomer having an amino group include 2-aminoethyl acrylate and 2-aminomethyl methacrylate.
Examples of the monomer having a phenolic hydroxyl group include hydroxystyrene, N- (hydroxyphenyl) acrylamide, N- (hydroxyphenyl) methacrylamide, and N- (hydroxyphenyl) maleimide.
Examples of the monomer having an isocyanate group include acryloyloxyethyl isocyanate, methacryloyloxyethyl isocyanate, and m-tetramethylxylene diisocyanate.
In the side chain represented by the formula (b 2) thus obtained, R is 51 Specific examples of (A) include the following formula (B-1)The expression (B-11) and the like.
Figure BDA0001405366870000181
In the present invention, when the polymer (specific copolymer 2) which is the component (B) in example 1 is to be obtained, a monomer copolymerizable with the specific monomer X1 and the specific monomer X3 and having no substituent capable of thermal crosslinking as described above may be used in combination.
Specific examples of such monomers include acrylate compounds or methacrylate compounds having different structures from the specific monomer X1 and the specific monomer X3, maleimide compounds, acrylamide compounds, acrylonitrile, maleic anhydride, styrene compounds, vinyl compounds, and the like (hereinafter, also referred to as a monomer X4).
Specific examples of the monomer X4 are shown below, but not limited thereto.
Examples of the acrylate compound as the monomer X4 include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl methyl acrylate, phenyl acrylate, glycidyl acrylate, 2-trifluoroethyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and 8-ethyl-8-tricyclodecyl acrylate.
Examples of the methacrylate compound as the monomer X4 include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, phenyl methacrylate, glycidyl methacrylate, 2-trifluoroethyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, γ -butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate.
Examples of the vinyl compound as the monomer X4 include methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl carbazole, allyl glycidyl ether, 3-vinyl-7-oxabicyclo [4.1.0] heptane, 1, 2-epoxy-5-hexene, and 1, 7-octadiene monoepoxide.
Examples of the styrene compound as the monomer X4 include styrene, methylstyrene, chlorostyrene, bromostyrene and the like.
Examples of the maleimide compound as the monomer X4 include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.
In the polymer (specific copolymer 2) as the component 1 of the component (B), the proportion of the N-alkoxyalkyl group present is preferably 40 to 90 mol%, more preferably 50 to 85 mol%, based on 100 mol of the total repeating units of the polymer.
That is, the amount of the specific monomer X1 used to obtain the specific copolymer 2 as the component (B) 1 example is preferably 40 to 90 mol%, and more preferably 50 to 85 mol%, based on the total amount of all the monomers used to obtain the specific copolymer 2 as the component (B) 1 example.
When the amount is less than 40 mol% of the total amount, thermal crosslinking curing with the component (A) may be insufficient, and when it is more than 90 mol%, adhesion to the substrate may be adversely affected.
In the polymer (specific copolymer 2) as the component 1 example of the component (B), the side chain group containing a polymerizable C = C double bond is present in a proportion of preferably 10 to 60 mol%, more preferably 15 to 50 mol%, based on 100 mol of all repeating units in the polymer.
That is, the amount of the specific monomer X3 used to obtain the specific copolymer 2 as the component (B) 1 example is preferably 10 to 60 mol%, more preferably 15 to 50 mol%, based on the total amount of all the monomers used to obtain the specific copolymer 2 as the component (B) 1 example.
When the total amount is less than 10 mol%, the adhesion of the liquid crystal layer may be insufficient, and when the amount is more than 60 mol%, the thermal crosslinking curing with the component (a) may be insufficient.
The method for obtaining the specific copolymer 2 as the component 1 of the component (B) is not particularly limited, and for example, it can be obtained by polymerizing the specific monomer X1, the specific monomer X3 and, if necessary, another monomer used, for example, the monomer X4 and a polymerization initiator in a solvent in which these monomers coexist at a temperature of 50 to 110 ℃. The solvent used in this case is not particularly limited as long as it can dissolve the monomer represented by the formula X, other monomers used as desired, a polymerization initiator, and the like. Specific examples thereof include those described in the item < solvent > described later.
The acrylic polymer as an example of the specific copolymer 2 obtained by the above method is usually in a solution state dissolved in a solvent, and can be used as it is as a solution of the component (B) in the present invention.
Further, the solution of the acrylic polymer as an example of the specific copolymer 2 obtained by the above-mentioned method is put into stirred ether, water or the like to reprecipitate, and the formed precipitate is filtered and washed, and then dried at normal temperature or under reduced pressure or dried by heating to obtain a powder of the specific copolymer 2 as an example of the component 1 (B). By the above-described operation, the polymerization initiator and the unreacted monomer which coexist with the specific copolymer 2 of the component (B) 1 example can be removed, and as a result, the purified powder of the specific copolymer 2 of the component (B) 1 example can be obtained. When the purification was not sufficiently carried out by 1 operation, the obtained powder was redissolved in a solvent and the above operation was repeated.
In the composition for forming a surface-cured film of an optical film of the present invention, the specific copolymer 2 as the component 1 (B) can be used in the form of a powder or a solution prepared by redissolving a purified powder in a solvent described later.
In the composition for forming a surface-cured film of the optical film of the present invention, the specific copolymer 2 as the component 1 (B) may be a mixture of a plurality of types.
The weight average molecular weight of such a polymer is 1,000 to 500,000, preferably 2,000 to 200,000, more preferably 3,000 to 150,000, and still more preferably 3,000 to 50,000.
The content of the crosslinking agent as the component (B) in the composition for forming a cured film of the present invention is preferably 1 to 600 parts by mass, and more preferably 5 to 400 parts by mass based on 100 parts by mass of the compound as the component (a). When the content of the crosslinking agent is too small, the solvent resistance of a cured film obtained from the composition for forming a cured film is lowered, and the vertical alignment property is lowered. On the other hand, when the content is too large, the vertical alignment property and the storage stability may be lowered.
< ingredient (C) >
The cured film-forming composition of the present invention may contain a polymer having a thermally crosslinkable group as the component (C). The thermally crosslinkable group here means a carboxyl group, a hydroxyl group, an amino group having an active hydrogen, a phenolic hydroxyl group, a hydroxymethyl group, an ester, an imide, or the like.
Examples of the polymer of component (C) include acrylic polymers, polyamic acids, polyimides, polyvinyl alcohols, polyesters, polyester polycarboxylic acids, polyether polyols, polyester polyols, polycarbonate polyols, polycaprolactone polyols, polyalkylene imines, polyallylamines, celluloses (cellulose or derivatives thereof), polymers having a linear structure or a branched structure such as phenol novolac resins and melamine formaldehyde resins, and cyclic polymers such as cyclodextrins.
Preferred examples of the polymer having a thermally crosslinkable group as the component (C) include acrylic polymers, hydroxyalkyl cyclodextrins, celluloses, polyether polyols, polyester polyols, polycarbonate polyols, and polycaprolactone polyols.
The acrylic polymer, which is a preferred example of the polymer having a thermally crosslinkable group as the component (C), is a polymer obtained by polymerizing a monomer having an unsaturated double bond such as acrylic acid, methacrylic acid, styrene, or a vinyl compound, and is not particularly limited as long as it is a polymer obtained by polymerizing a monomer having a thermally crosslinkable group or a mixture containing the monomer.
Examples of the monomer having a thermally crosslinkable group include a monomer having a polyethylene glycol ester group, a monomer having a hydroxyalkyl ester group having 2 to 5 carbon atoms, a monomer having a phenolic hydroxyl group, a monomer having a carboxyl group, a monomer having an amino group, and a monomer having an alkoxysilyl group and a group represented by the above formula 2.
Examples of the monomer having a polyethylene glycol ester group include H- (OCH) 2 CH 2 ) Monoacrylates or monomethacrylates of n-OH. The value of n is 2 to 50, preferably 2 to 10.
Examples of the monomer having a hydroxyalkyl ester group having 2 to 5 carbon atoms include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate and 4-hydroxybutyl methacrylate.
Examples of the monomer having a phenolic hydroxyl group include p-hydroxystyrene, m-hydroxystyrene and o-hydroxystyrene.
Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, and vinylbenzoic acid.
Examples of the monomer having an amino group in a side chain include 2-aminoethyl acrylate, 2-aminoethyl methacrylate, aminopropyl acrylate and aminopropyl methacrylate.
Examples of the monomer having the alkoxysilyl group in the side chain include 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, and allyltriethoxysilane.
Examples of the monomer having a group represented by the formula 2 in the side chain include 2-acetoacetoxyethyl acrylate and 2-acetoacetoxyethyl (meth) acrylate.
In the present embodiment, when an acrylic polymer as an example of the component (C) is synthesized, a monomer not having any of a hydroxyl group, a carboxyl group, an amide group, an amino group, an alkoxysilyl group, and a group represented by the above formula 2 may be used in combination as long as the effect of the present invention is not impaired.
Specific examples of such monomers include acrylate compounds, methacrylate compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds, vinyl compounds, and the like.
Examples of the acrylate compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl methyl acrylate, phenyl acrylate, 2-trifluoroethyl acrylate, t-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and 8-ethyl-8-tricyclodecyl acrylate.
Examples of the methacrylate compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, phenyl methacrylate, 2-trifluoroethyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate.
Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.
Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, and bromostyrene.
Examples of the vinyl compound include vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether.
The amount of the monomer having a thermally crosslinkable group used for obtaining the acrylic polymer as an example of the component (C) is preferably 2 to 98 mol% based on the total amount of all the monomers used for obtaining the acrylic polymer as the component (C). When the monomer having a thermally crosslinkable group is too small, the liquid crystal alignment property of the resulting cured film tends to be insufficient, and when it is too large, the compatibility with the component (a) tends to be lowered.
The method for obtaining the acrylic polymer as an example of the component (C) is not particularly limited, and for example, it can be obtained by polymerizing a monomer having a thermal crosslinkable group, a monomer having no thermal crosslinkable group used as desired, and a polymerization initiator in a solvent in which these monomers coexist at a temperature of 50 to 110 ℃. The solvent used in this case is not particularly limited as long as it can dissolve the monomer having a thermally crosslinkable group, the monomer having no thermally crosslinkable group used as desired, the polymerization initiator, and the like. Specific examples are described in the item < solvent > described later.
The acrylic polymer as an example of the component (C) obtained by the above-mentioned method is usually in a solution state dissolved in a solvent.
Further, the acrylic polymer solution as an example of the component (C) obtained by the above-mentioned method is put into stirred ether, water or the like to reprecipitate, and the resultant precipitate is filtered and washed, and then dried at normal temperature or under reduced pressure or dried by heating to obtain a powder of the acrylic polymer as an example of the component (C). By the above-described operation, the polymerization initiator and the unreacted monomer which coexist with the acrylic polymer as the component (C) can be removed, and as a result, a purified powder of the acrylic polymer as the component (C) can be obtained. When the purification was not sufficiently performed by 1 operation, the obtained powder was redissolved in a solvent and the above operation was repeated.
(C) The acrylic polymer is a preferable example of the component (B), and the weight average molecular weight is preferably 3000 to 200000, more preferably 4000 to 150000, and further preferably 5000 to 100000. When the weight average molecular weight is more than 200000, the solubility in a solvent may be lowered and the handling property may be lowered, and when the weight average molecular weight is more than 3000, the curing may be insufficient at the time of thermal curing, and the solvent resistance and heat resistance may be lowered. The weight average molecular weight is a value obtained by Gel Permeation Chromatography (GPC) using polystyrene as a standard sample. The same applies to the following description.
Next, as a preferable example of the polyether polyol as the polymer having a thermally crosslinkable group as the component (C), polyethylene glycol, polypropylene glycol, or a compound obtained by adding a polyvalent alcohol such as propylene glycol, bisphenol a, triethylene glycol, or sorbitol to ethylene oxide, polyethylene glycol, polypropylene glycol, or the like can be cited. Specific examples of polyether polyols include: wo 124591245912509125125125125225612540\\\ 12486125581245812412412440, HC-60, ST-30E, ST-40E, G-450, G-750, v 12518and v-1241241241241245818, ch-12463tg-4000, HS-1241600D, DA-400, DA-700, DB-400, 124949194\\\\\\\\ 1255812540125 (registered trademark).
Examples of the polyester polyol which is a preferable example of the polymer having a thermally crosslinkable group as the component (C) include those obtained by reacting a polycarboxylic acid such as adipic acid, sebacic acid, or isophthalic acid with a glycol such as ethylene glycol, propylene glycol, butylene glycol, polyethylene glycol, or polypropylene glycol. Specific examples of the polyester polyol include those prepared by DIC (registered trademark) Nos. \12509125221251251, OD-X-355, OD-X-2330, OD-X-240, OD-X-668, OD-X-2108, OD-X-2376, OD-X-2044, OD-X-688, OD-X-2068, OD-X-2547, OD-X-2420, OD-X-2523, OD-X-2555, OD-X-2560 and OD 12463125211252460 (trademark) and polyhydric alcohols P-510, P-1010, P-6012010, P-3010, P-4010, P-5010, P-501510, F-1010, F-2010, F-3010, P-1011, P-2013, P-2012016, and N-2016.
The polycaprolactone polyol which is a preferable example of the polymer having a thermally crosslinkable group as the component (C) includes a polymer obtained by ring-opening polymerization of epsilon-caprolactone using trimethylolpropane, a polyvalent alcohol such as ethylene glycol, or the like as an initiator. Specific examples of the polycaprolactone polyol include compounds prepared by general chemical methods known in DIC Nos. 1250912521\\\1245288 (registered trademark) OD-X-2155, OD-X-640, OD-X-2568 and 12480\\124527512523232323232323232323205 (registered trademark) 1250312503125125125125125632323205, L205AL, 205U, 208, 210, 212, L212AL, 220, 230, 240, 303, 305, 308, 312 and 320.
Examples of the polycarbonate polyol which is a preferable example of the polymer having a thermally crosslinkable group as the component (C) include polymers obtained by reacting a polyvalent alcohol such as trimethylolpropane or ethylene glycol with diethyl carbonate, diphenyl carbonate, ethylene carbonate, and the like. Specific examples of the polycarbonate polyols include compounds represented by the general formulae (i) v.v. \\ 124801245275125231252112463.
Examples of preferable cellulose as the polymer having a thermally crosslinkable group as the component (C) include hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose, hydroxyalkyl alkylcelluloses such as hydroxyethyl methylcellulose, hydroxypropyl methylcellulose and hydroxyethyl ethylcellulose, and cellulose, and preferable examples are hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose.
Preferred examples of the cyclodextrin as the polymer having a thermally crosslinkable group as the component (C) include cyclodextrins such as α -cyclodextrin, β -cyclodextrin and γ -cyclodextrin, methylated cyclodextrins such as methyl- α -cyclodextrin, methyl- β -cyclodextrin and methyl- γ -cyclodextrin, hydroxymethyl- α -cyclodextrin, hydroxymethyl- β -cyclodextrin, hydroxymethyl- γ -cyclodextrin, 2-hydroxyethyl- α -cyclodextrin, 2-hydroxyethyl- β -cyclodextrin, 2-hydroxyethyl- γ -cyclodextrin, 2-hydroxypropyl- α -cyclodextrin, 2-hydroxypropyl- β -cyclodextrin, 2-hydroxypropyl- γ -cyclodextrin, 3-hydroxypropyl- α -cyclodextrin, 3-hydroxypropyl- β -cyclodextrin, 3-hydroxypropyl- γ -cyclodextrin, 2, 3-dihydroxypropyl- α -cyclodextrin, 2, 3-dihydroxypropyl- β -cyclodextrin and hydroxyalkyl-cyclodextrin.
A melamine-formaldehyde resin, which is a preferable example of the polymer having a thermally crosslinkable group as the component (C), is a resin obtained by polycondensation of melamine and formaldehyde, and is represented by the following formula.
Figure BDA0001405366870000271
In the above formula, R 21 Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n is a natural number representing the number of repeating units.
(C) A melamine-formaldehyde resin is a preferred example of the component (A), and a resin in which methylol groups formed by polycondensation of melamine and formaldehyde are O-alkylated is preferred from the viewpoint of storage stability.
A preferable example of the method for obtaining the melamine-formaldehyde resin as the component (C) is not particularly limited, and the melamine-formaldehyde resin is generally synthesized by mixing melamine and formaldehyde, making the mixture weakly alkaline with sodium carbonate, ammonia or the like, and then heating the mixture at 60 to 100 ℃. Further, the methylol group can be alkoxylated by reaction with an alcohol.
(C) The melamine formaldehyde resin is preferably a melamine formaldehyde resin having a weight average molecular weight of preferably 250 to 5000, more preferably 300 to 4000, and still more preferably 350 to 3500. When the weight average molecular weight is far greater than 5000, the solubility in a solvent may be lowered, the handling properties may be lowered, and when the weight average molecular weight is less than 250 and too small, curing may be insufficient during heat curing, and the effect of improving solvent resistance and heat resistance may not be sufficiently exhibited.
The melamine formaldehyde resin, which is a preferable example of the component (C) in the embodiment of the present invention, may be used in the form of a liquid or a solution obtained by redissolving a purified liquid in a solvent to be described later.
As a preferable example of the polymer having a thermally crosslinkable group as the component (C), there can be mentioned, for example, a phenol novolac resin, and a phenol-formaldehyde polycondensate.
In the composition for forming a cured film of the present embodiment, the polymer having a thermally crosslinkable group as the component (C) may be used in the form of a powder or a solution obtained by redissolving a purified powder in a solvent to be described later.
The content of the component (C) in the cured film-forming composition of the present invention is preferably 400 parts by mass or less, more preferably 10 to 380 parts by mass, and still more preferably 40 to 360 parts by mass, based on 100 parts by mass of the total amount of the compound as the component (a) and the crosslinking agent as the component (B). (C) When the content of the component is too large, the liquid crystal alignment property is liable to be lowered, and when it is too small, the adhesiveness is liable to be lowered.
In the composition for forming a cured film according to the present embodiment, the component (C) may be a mixture of a plurality of polymers exemplified as the component (C).
< ingredient (D) >
The composition for forming a cured film of the present invention may further contain a crosslinking catalyst as the component (D) in addition to the components (A) and (B).
As the crosslinking catalyst of the component (D), for example, an acid or a thermal acid generator can be preferably used. The component (D) is effective for promoting the heat curing reaction of the cured film-forming composition of the present invention.
Specific examples of the component (D) include sulfonic acid group-containing compounds as the above-mentioned acids, hydrochloric acid, and salts thereof. The thermal acid generator is not particularly limited as long as it is a compound that can generate an acid by thermal decomposition during heat treatment, that is, a compound that generates an acid by thermal decomposition at a temperature of 80 to 250 ℃.
Specific examples of the acid include hydrochloric acid or a salt thereof; sulfonic acid group-containing compounds such as methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, octanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, camphorsulfonic acid, trifluoromethanesulfonic acid, p-hydroxybenzenesulfonic acid, 2-naphthalenesulfonic acid, 1,3, 5-trimethylbenzenesulfonic acid, p-xylene-2-sulfonic acid, m-xylene-2-sulfonic acid, 4-ethylbenzenesulfonic acid, 1H, 2H-perfluorooctanesulfonic acid, perfluoro (2-ethoxyethane) sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutane-1-sulfonic acid, dodecylbenzenesulfonic acid, and hydrates, salts thereof, and the like.
Further, examples of the compound capable of generating an acid by heat include bis (tosyloxy) ethane, bis (tosyloxy) propane, bis (tosyloxy) butane, p-nitrobenzyl tosylate, o-nitrobenzyl tosylate, 1,2, 3-benzenetris (methylsulfonate), and p-toluenesulfonate pyridine
Figure BDA0001405366870000281
Salt, morpholine p-toluenesulfonate
Figure BDA0001405366870000282
Salts, ethyl p-toluenesulfonate, propyl p-toluenesulfonate, butyl p-toluenesulfonate, isobutyl p-toluenesulfonate, methyl p-toluenesulfonate, phenethyl p-toluenesulfonate, cyanomethyl p-toluenesulfonate, 2-trifluoroethyl p-toluenesulfonateTosylate, 2-hydroxybutyl-p-toluenesulfonate, N-ethyl-p-toluenesulfonamide, and a compound represented by the following formula.
Figure BDA0001405366870000291
Figure BDA0001405366870000301
Figure BDA0001405366870000311
The content of the component (D) in the composition for forming a cured film of the present invention is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, and still more preferably 0.5 to 10 parts by mass, based on 100 parts by mass of the total amount of the compound as the component (a) and the crosslinking agent as the component (B). By setting the content of the component (D) to 0.01 parts by mass or more, sufficient thermosetting property and solvent resistance can be provided. However, if the amount is more than 20 parts by mass, the storage stability of the composition may be lowered.
The present invention may further contain a component (adhesion-improving component) for improving the adhesion of the formed cured film as the component (E).
When the cured film formed from the composition for forming a cured film of the present embodiment containing the component (E) is used as an alignment material, the polymerizable functional group of the polymerizable liquid crystal and the crosslinking reaction site of the alignment material can be covalently bonded to each other, and the adhesion between the alignment material and the layer of the polymerizable liquid crystal can be improved. As a result, the retardation material of the present embodiment in which the cured polymerizable liquid crystal is laminated on the alignment material of the present embodiment can maintain strong adhesion even under high-temperature and high-humidity conditions, and exhibit high durability against peeling or the like.
The component (E) is preferably a compound having a group selected from a hydroxyl group and an N-alkoxymethyl group, and a polymerizable group.
Examples of the component (E) include compounds having a hydroxyl group and a (meth) acryloyl group, compounds having an N-alkoxymethyl group and a (meth) acryloyl group, and polymers having an N-alkoxymethyl group and a (meth) acryloyl group. Hereinafter, specific examples thereof are shown, respectively.
As an example of the component (E), a hydroxyl group-containing polyfunctional acrylate (hereinafter, also referred to as hydroxyl group-containing polyfunctional acrylate) can be cited.
Examples of the hydroxyl group-containing polyfunctional acrylate as the component (E) include pentaerythritol triacrylate and dipentaerythritol pentaacrylate.
An example of the component (E) is a compound having 1 acryloyl group and 1 or more hydroxyl groups. Preferred examples of such a compound having 1 acryloyl group and 1 or more hydroxyl groups are mentioned. The compound of component (E) is not limited to the following compound examples.
Figure BDA0001405366870000331
(in the formula, R 11 Represents a hydrogen atom or a methyl group, and m represents an integer of 1 to 10. )
Further, as the compound of the component (E), a compound having at least 1 group containing a polymerizable C = C double bond and at least 1N-alkoxymethyl group in 1 molecule is exemplified.
Examples of the group having a polymerizable C = C double bond include an acryloyl group, a methacryloyl group, a vinyl group, an allyl group, and a maleimide group.
Examples of the N, i.e., nitrogen atom of the N-alkoxymethyl group include an amide nitrogen atom, a thioamide nitrogen atom, a urea nitrogen atom, a thiourea nitrogen atom, a carbamate nitrogen atom, a nitrogen atom bonded to the ortho-position of the nitrogen atom of the nitrogen-containing heterocycle, and the like. Thus, the N-alkoxymethyl group may have a structure in which an alkoxymethyl group is bonded to a nitrogen atom selected from the group consisting of an amide nitrogen atom, a thioamide nitrogen atom, a urea nitrogen atom, a thiourea nitrogen atom, a carbamate nitrogen atom, a nitrogen atom bonded to the nitrogen atom of a nitrogen-containing heterocyclic ring in the ortho-position, and the like.
The component (E) may have the above-mentioned group, but preferably includes, for example, a compound represented by the above-mentioned formula (X1).
As another form of the compound having a group containing a polymerizable C = C double bond and an N-alkoxymethyl group as the component (E), for example, a compound represented by the following formula (X2) is preferably exemplified.
Figure BDA0001405366870000341
In the formula, R 51 Represents a hydrogen atom or a methyl group.
R 52 Represents an alkyl group having 2 to 20 carbon atoms, a 1-valent aliphatic ring group having 5 to 6 carbon atoms, or a 1-valent aliphatic group containing an aliphatic ring having 5 to 6 carbon atoms, and may contain an ether bond in its structure.
R 53 Represents a linear or branched alkylene group having 2 to 20 carbon atoms, a 2-valent aliphatic ring group having 5 to 6 carbon atoms, or a 2-valent aliphatic group containing an aliphatic ring having 5 to 6 carbon atoms, and may contain an ether bond in its structure.
R 54 Represents a linear or branched aliphatic group having 2 to 9 valences and having 1 to 20 carbon atoms, an aliphatic ring group having 2 to 9 valences and having 5 to 6 carbon atoms, or an aliphatic ring having 2 to 9 valences and having 5 to 6 carbon atoms, and one methylene group or a plurality of non-adjacent methylene groups in these groups may be replaced by an ether bond.
Z represents > NCOO-, OR-OCON < (where "-" represents 1 linkage. Furthermore, ">", "<" represents 2 linkages, and represents 1 linkage in which an alkoxymethyl group is bonded (i.e., -OR) 52 A base). ).
r is a natural number of 2 to 9.
As R 53 Specific examples of the alkylene group having 2 to 20 carbon atoms in the definition of (1) above includeA 2-valent group obtained by further removing 1 hydrogen atom from an alkyl group having 2 to 20 carbon atoms.
Furthermore as R 54 Specific examples of the 2-to 9-valent aliphatic group having 1 to 20 carbon atoms in the definition of (a) include 2-to 9-valent groups obtained by further removing 1 to 8 hydrogen atoms from an alkyl group having 1 to 20 carbon atoms.
Examples of the alkyl group having 1 carbon atom include a methyl group, and examples thereof include an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a1, 1-dimethyl-n-propyl group, an n-hexyl group, a 1-methyl-n-pentyl group, a 2-methyl-n-pentyl group, a1, 1-dimethyl-n-butyl group, a 1-ethyl-n-butyl group, a1, 2-trimethyl-n-propyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group, an n-octadecyl group, an n-nonadecyl group, an n-eicosyl group, a cyclopentyl group, a cyclohexyl group, and a group in which one or more of these groups are bonded within a range of 20 carbon atoms, and a group in which one or a plurality of methylene group is not substituted by ether bond.
Among these, an alkylene group having 2 to 10 carbon atoms is preferable, and R is particularly preferable from the viewpoint of the availability of raw materials and the like 53 Is ethylene, R 54 A hexylene group.
As R 52 Specific examples of the alkyl group having 1 to 20 carbon atoms in the definition of (1) include R 53 Specific examples of the alkyl group having 2 to 20 carbon atoms in the definition of (1) and methyl group. Among these, an alkyl group having 1 to 6 carbon atoms is preferable, and a methyl group, an ethyl group, an n-propyl group, or an n-butyl group is particularly preferable.
R is a natural number of 2 to 9, and among these, 2 to 6 are preferable.
The compound (X2) can be obtained by a production method represented by the following reaction formula. That is, an amino group having an acryloyl group or a methacryloyl group represented by the following formula (X2-1)A formate compound (hereinafter, also referred to as compound (X2-1)) is reacted in a solvent to which trimethylchlorosilane and paraformaldehyde are added to synthesize an intermediate represented by the following formula (X2-2), and R is added to the reaction solution 52 An alcohol represented by-OH, thereby producing the compound.
Figure BDA0001405366870000351
In the formula, R 51 、R 52 、R 53 、R 54 Z and r have the meanings given above, and X represents-NHCOO-or-OCONH-.
The amount of trimethylchlorosilane and paraformaldehyde used relative to the compound (X2-1) is not particularly limited, but for the purpose of completing the reaction, 1.0 to 6.0 equivalent times of trimethylchlorosilane and 1.0 to 3.0 equivalent times of paraformaldehyde are preferably used relative to 1 urethane bond in the molecule, and more preferably the amount of trimethylchlorosilane used is larger than the amount of paraformaldehyde used.
The reaction solvent is not particularly limited as long as it is inert to the reaction, and examples thereof include hydrocarbons such as hexane, cyclohexane, benzene, and toluene; halogenated hydrocarbons such as methylene chloride, carbon tetrachloride, chloroform, 1, 2-dichloroethane; ethers such as diethyl ether, diisopropyl ether, 1, 4-dioxane and tetrahydrofuran; nitriles such as acetonitrile and propionitrile; nitrogen-containing aprotic polar solvents such as N, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, and 1, 3-dimethyl-2-imidazolidinone; pyridines such as pyridine and picoline. These solvents may be used alone, or 2 or more of these solvents may be used in combination. Dichloromethane and chloroform are preferred, and dichloromethane is more preferred.
The amount of the solvent used (reaction concentration) is not particularly limited, and the reaction may be carried out without using a solvent, and when a solvent is used, the amount of the solvent may be 0.1 to 100 times by mass based on the compound (X2-1). Preferably 1 to 30 times by mass, and more preferably 2 to 20 times by mass.
The reaction temperature is not particularly limited, and examples thereof include-90 to 200 ℃, preferably-20 to 100 ℃, and more preferably-10 to 50 ℃.
The reaction time is usually 0.05 to 200 hours, preferably 0.5 to 100 hours.
The reaction can be carried out under normal pressure or under pressure, and may be carried out batchwise or continuously.
A polymerization inhibitor may be added during the reaction. Such a polymerization inhibitor may be BHT (2, 6-di-t-butyl-p-cresol), hydroquinone, p-methoxyphenol, or the like, and is not particularly limited as long as it can prevent polymerization of an acryloyl group or a methacryloyl group.
The amount of the polymerization inhibitor to be added is not particularly limited, but is 0.0001 to 10wt%, preferably 0.01 to 1wt%, based on the total amount (mass) of the compound (X2-1) used. In the present specification, wt% means mass%.
In the step of reacting the intermediate (X2-2) with an alcohol, a base may be added to suppress hydrolysis under acidic conditions. Examples of the base include pyridines such as pyridine and picoline, and tertiary amines such as trimethylamine, triethylamine, diisopropylethylamine, and tributylamine. Triethylamine, diisopropylethylamine and triethylamine are preferred. The amount of the base to be added is not particularly limited, but is preferably 0.01 to 2.0 equivalents, more preferably 0.5 to 1.0 equivalent, based on the amount of trimethylchlorosilane to be used in the reaction.
Further, after obtaining intermediate (X2-2) from compound (X2-1), an alcohol may be added to carry out the reaction without isolating intermediate (X2-2).
The method for synthesizing the compound (X2-1) is not particularly limited, and it can be produced by reacting a (meth) acryloyloxyalkyl isocyanate with a polyol compound or by reacting a hydroxyalkyl (meth) acrylate compound with a polyisocyanate compound.
Specific examples of the (meth) acryloyloxyalkyl isocyanate include, for example, 2-methacryloyloxyethyl isocyanate (trade names: 12459125241252474moi [ registered trademark ]), 2-acryloyloxyethyl isocyanate (trade names: 12459125247490.
Specific examples of the polyol compound include glycol compounds such as ethylene glycol, propylene glycol, 1, 4-butanediol, 1, 3-butanediol, 1, 5-pentanediol, neopentyl glycol, 3-methyl-1, 5-pentanediol, 1, 6-hexanediol, and 1, 4-cyclohexanedimethanol, triol compounds such as glycerin and trimethylolpropane, pentaerythritol, dipentaerythritol, and diglycerol.
Specific examples of the hydroxyalkyl (meth) acrylate compound include monomers having a hydroxyl group such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, poly (ethylene glycol) ethyl ether acrylate, and poly (ethylene glycol) ethyl ether methacrylate.
Specific examples of the polyisocyanate compound include aliphatic diisocyanates such as hexamethylene diisocyanate, 2, 4-trimethylhexamethylene diisocyanate and dimer acid diisocyanate, alicyclic diisocyanates such as isophorone diisocyanate, 4 '-methylenebis (cyclohexyl isocyanate) and ω, ω' -diisocyanate dimethylcyclohexane, triisocyanate compounds such as lysyl diisocyanate, 1,6, 11-undecane triisocyanate, 1, 8-diisocyanate-4-isocyanatomethyloctane, 1,3, 6-hexamethylene triisocyanate and bicycloheptane triisocyanate, and the like.
These (meth) acryloyloxyalkyl isocyanate compounds, polyol compounds, hydroxyalkyl (meth) acrylate compounds and polyisocyanate compounds are generally commercially available, and can be synthesized by a known method.
The content of the component (E) in the cured film-forming composition according to the embodiment of the present invention is preferably 0.1 to 100 parts by mass, more preferably 5 to 70 parts by mass, based on 100 parts by mass of the total amount of the compound as the component (a) and the crosslinking agent as the component (B). By setting the content of the component (E) to 0.1 part by mass or more, sufficient adhesion can be imparted to the formed cured film. However, if the amount is more than 100 parts by mass, the liquid crystal alignment property tends to be lowered.
In the composition for forming a cured film according to the present embodiment, the component (E) may be a mixture of a plurality of compounds of the component (E).
< solvent >
The composition for forming a cured film of the present invention is mainly used in the form of a solution dissolved in a solvent. The solvent used in this case is not particularly limited in kind, structure, and the like, as long as it can dissolve the component (a), the component (B), and if necessary, the component (C), the component (D), the component (E), and/or other additives described later.
<xnotran> , , , , , , , ,2- -1- , , , , , , , , , , , , , , , , , , , , ,2- ,3- -2- ,2- ,2- , γ - ,2- ,2- -2- , , ,2- -3- ,3- ,3- ,3- ,3- , , , , , , , , N, N- , N, N- , N- -2- . </xnotran>
In the case of producing an alignment material by forming a cured film on a resin film using the composition for forming a cured film of the present invention, methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-methyl-1-butanol, 2-heptanone, isobutyl methyl ketone, diethylene glycol, propylene glycol monomethyl ether acetate and the like are preferred as solvents which exhibit resistance to the resin film.
These solvents may be used in 1 kind alone or in combination of 2 or more kinds.
< other additives >
The composition for forming a cured film of the present invention may further contain, as required, a sensitizer, an adhesion improver, a silane coupling agent, a surfactant, a rheology modifier, a pigment, a dye, a storage stabilizer, an antifoaming agent, an antioxidant, and the like as long as the effects of the present invention are not impaired.
For example, the sensitizer is effective for promoting photoreaction after a thermosetting film is formed using the resin composition for forming a retardation material of the present invention.
Examples of the sensitizer as another additive include benzophenone, anthracene, anthraquinone, thioxanthone, derivatives thereof, and nitrophenyl compounds. Among them, benzophenone derivatives and nitrophenyl compounds are preferable. Specific examples of preferable compounds include N, N-diethylaminobenzophenone, 2-nitrofluorene, 2-nitrofluorenone, 5-nitroacenaphthylene, 4-nitrobiphenyl, 4-nitrocinnamic acid, 4-nitrostilbene, 4-nitrobenzophenone, and 5-nitroindole. N, N-diethylaminobenzophenone is particularly preferable as a derivative of benzophenone.
The sensitizer is not limited to the foregoing. Further, the sensitizer may be used alone, or 2 or more compounds may be used in combination.
The proportion of the sensitizer used in the resin composition for forming a retardation material of the present invention is preferably 0.1 to 20 parts by mass, and more preferably 0.2 to 10 parts by mass, based on 100 parts by mass of the total of the components (a) to (E). When the ratio is too small, a sufficient effect as a sensitizer may not be obtained, and when it is too large, a decrease in transmittance and roughness of a coating film may occur.
< preparation of composition for Forming cured film >
The composition for forming a cured film of the present invention contains a compound as the component (a) and a crosslinking agent as the component (B), and may contain a polymer having a thermally crosslinkable group as the component (C), a crosslinking catalyst as the component (D), and an adhesion-improving component as the component (E) if necessary, and may contain other additives within limits not detrimental to the effects of the present invention. They are generally used in the form of solutions dissolved in solvents.
Preferred examples of the composition for forming a cured film of the present invention are as follows.
[1]: a composition for forming a cured film, which comprises component (A), component (B) in an amount of 1 to 300 parts by mass based on 100 parts by mass of component (A), and component (C) in an amount of 1 to 400 parts by mass based on 100 parts by mass of the total amount of the compound of component (A) and the crosslinking agent of component (B).
[2]: a composition for forming a cured film, which comprises a component (A), a component (B) in an amount of 1 to 600 parts by mass based on 100 parts by mass of the component (A), a component (C) in an amount of 1 to 400 parts by mass based on 100 parts by mass of the total amount of a compound as the component (A) and a crosslinking agent as the component (B), and a solvent.
[3]: a composition for forming a cured film, which comprises (A) component, 1 to 600 parts by mass of (B) component based on 100 parts by mass of (A) component, 1 to 400 parts by mass of (C) component based on 100 parts by mass of the total amount of the compound as (A) component and the crosslinking agent as (B) component, 0.01 to 20 parts by mass of (D) component based on 100 parts by mass of the total amount of the compound as (A) component and the crosslinking agent as (B) component, and a solvent.
[4]: a composition for forming a cured film, which comprises (A) component, 1 to 600 parts by mass of (B) component based on 100 parts by mass of (A) component, 1 to 400 parts by mass of (C) component based on 100 parts by mass of the total amount of a compound as (A) component and a crosslinking agent as (B) component, 0.01 to 20 parts by mass of (D) component based on 100 parts by mass of the total amount of a compound as (A) component and a crosslinking agent as (B) component, 0.1 to 100 parts by mass of (E) component based on 100 parts by mass of the total amount of a compound as (A) component and a crosslinking agent as (B) component, and a solvent.
The compounding ratio, preparation method and the like of the cured film-forming composition of the present invention when used as a solution will be specifically described below.
The proportion of the solid component in the cured film-forming composition of the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent, and may be 1 to 60 mass%, preferably 2 to 50 mass%, and more preferably 2 to 20 mass%. Here, the solid component refers to a component remaining after removing the solvent from all components of the cured film-forming composition.
The method for preparing the cured film-forming composition of the present invention is not particularly limited. Examples of the preparation method include a method of mixing the component (B) in a predetermined ratio into a solution of the component (a) dissolved in a solvent, and further mixing the component (C), the component (D), the component (E), and the like in predetermined ratios as necessary to form a uniform solution, and a method of further adding and mixing other additives as necessary at an appropriate stage of the preparation method.
In the preparation of the composition for forming a cured film of the present invention, a solution of the specific copolymer (polymer) obtained by polymerization reaction in a solvent may be used as it is. In this case, for example, the component (B) may be added to the solution of the component (A) in the same manner as described above, and if necessary, the components (C), (D), and (E) may be added to form a uniform solution. In this case, a solvent may be further added to adjust the concentration. In this case, the solvent used in the process of producing the component (a) may be the same as or different from the solvent used in the concentration adjustment of the cured film-forming composition.
The solution of the prepared cured film-forming composition is preferably filtered using a filter having a pore size of about 0.2 μm and the like, and then used.
< cured film, alignment material and phase difference material >
The solution of the composition for forming a cured film of the present invention can be applied to a substrate (for example, a silicon/silica-coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, chromium, or the like, a glass substrate, a quartz substrate, an ITO substrate, or the like), a film substrate (for example, a resin film such as a triacetyl cellulose (TAC) film, a Polycarbonate (PC) film, a cycloolefin polymer (COP) film, a cycloolefin copolymer (COC) film, a polyethylene terephthalate (PET) film, an acrylic film, a polyethylene film, or the like) by bar coating, spin coating, flow coating, roll coating, slit coating, and then spin coating, inkjet coating, printing, or the like to form a coating film, and then heat-dried by a hot plate, an oven, or the like to form a cured film. The cured film can be used as an alignment material.
The conditions for the heat drying may be such that the components of the cured film (alignment material) are not eluted from the polymerizable liquid crystal solution applied thereon, and the crosslinking reaction is carried out by the crosslinking agent, and for example, a heating temperature and a heating time appropriately selected from the range of 60 ℃ to 200 ℃ and the time range of 0.4 to 60 minutes can be used. The heating temperature and the heating time are preferably 70 to 160 ℃ for 0.5 to 10 minutes.
The thickness of the cured film (alignment material) formed using the composition for forming a cured film of the present invention is, for example, 0.05 to 5 μm, and can be appropriately selected in consideration of the difference in height of the substrate to be used, and the optical and electrical properties.
Since the alignment material formed from the cured film-forming composition of the present invention has solvent resistance and heat resistance, a retardation material such as a polymerizable liquid crystal solution having vertical alignment properties is applied to the alignment material, and the alignment material can be aligned. Further, by directly curing the retardation material in an oriented state, an optically anisotropic layer can be formed as the retardation material. When the substrate on which the alignment material is formed is a film, the film can be used as a retardation film.
Further, a liquid crystal display element in which liquid crystal is aligned can be formed by using 2 substrates formed as described above and having the alignment material of the present invention, bonding the alignment materials on both substrates so as to face each other with a spacer interposed therebetween, and then injecting liquid crystal between these substrates.
The composition for forming a cured film of the present invention can be suitably used for producing various retardation materials (retardation films), liquid crystal display devices, and the like.
Examples
Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited to these examples.
[ abbreviations used in the examples ]
The abbreviations used in the examples below have the following meanings.
< raw materials of the respective Components >
jER-828: bisphenol A epoxy resin prepared by Mitsubishi chemical corporation, molecular weight 370
jER-1001: bisphenol A epoxy resin prepared by Mitsubishi chemical corporation, molecular weight 900
TEPIC-L: 3-functional epoxy compound manufactured by Nissan chemical industry Co., ltd
MCA: p-methoxy cinnamic acid
PCA: para-propoxy cinnamic acid
MeCA: p-methyl cinnamic acid
FCA: para-fluorocinnamic acid
CA: cinnamic acid
BMAA: n-butoxymethylacrylamide
BTEAC: benzyl triethyl ammonium chloride
AIBN: alpha, alpha' -azobisisobutyronitrile
HEMA: 2-Hydroxyethyl methacrylate
MMA: methacrylic acid methyl ester
< ingredient (B) >
HMM: melamine crosslinking agents represented by the following structural formula [ \124699 (1245212513) \\ (CYMEL) (registered trademark) 303 (triwell 1246938 (manufactured by 124521248612463
Figure BDA0001405366870000431
< ingredient (D) >
PTSA:1 water and p-toluenesulfonic acid
< solvent >
PM: propylene glycol monomethyl ether
The number average molecular weight and the weight average molecular weight of the acrylic copolymer obtained in the following synthesis examples were measured under conditions in which tetrahydrofuran as an elution solvent was eluted at a flow rate of 1 mL/min in a column (column temperature 40 ℃) using GPC devices (Shodex (registered trademark) columns KF803L and KF804L, manufactured by japan spectrographic instruments. The number average molecular weight (hereinafter referred to as mn.) and the weight average molecular weight (hereinafter referred to as mw.) below represent polystyrene conversion values.
< Synthesis of component (A) >
< Synthesis example 1 >
20.9g of jER-828, 20.0g of MCA, and 0.26g of BTEAC were dissolved in 96.0g of PM, and reacted at 120 ℃ for 20 hours to obtain a photo-alignment compound (solid content concentration: 30 mass%) (PA 1). The epoxy value of the obtained compound was measured, and as a result, it was confirmed that an amount of epoxy groups that completely reacted MCA disappeared.
< Synthesis example 2 >
JeR-1001 53.2g, MCA 20.0g, and BTEAC 0.26g were dissolved in PM171.1g, and reacted at 120 ℃ for 20 hours to obtain a photo-alignment compound (solid content concentration 30 mass%) (PA 2). The epoxy value of the obtained compound was measured, and it was confirmed that an amount of epoxy groups that completely reacted MCA disappeared.
< Synthesis example 3 >
18.0g of jER-828, 20.0g of PCA, and 0.22g of BTEAC were dissolved in 89.3g of PM, and reacted at 120 ℃ for 20 hours to obtain a photo-alignment compound (solid content concentration: 30 mass%) (PA 3). The epoxy value of the obtained compound was measured, and it was confirmed that the epoxy group in an amount to complete the reaction of all PCA had disappeared.
< Synthesis example 4 >
20.9g of jER-828, 20.0g of MeCA, and 0.28g of BTEAC were dissolved in 96.3g of PM, and reacted at 120 ℃ for 20 hours to obtain a photo-alignment compound (solid content concentration: 30 mass%) (PA 4). The epoxy value of the obtained compound was measured, and it was confirmed that the epoxy group in an amount that all of the MeCA was reacted had disappeared.
< Synthesis example 5 >
jER-828 (20.5 g), FCA (20.0 g), and BTEAC (0.27 g) were dissolved in PM 95.1g, and reacted at 120 ℃ for 20 hours to obtain a photo-alignment compound (solid content concentration: 30 mass%) (PA 5). The epoxy value of the obtained compound was measured, and it was confirmed that the epoxy group in an amount that all FCA was reacted was disappeared.
< Synthesis example 6 >
TEPIC-L11.1 g, MCA 20.0g, and BTEAC 0.26g were dissolved in PM 73.2g, and reacted at 120 ℃ for 20 hours to obtain a photo-alignment compound (solid content concentration 30 mass%) (PA 6). The epoxy value of the obtained compound was measured, and as a result, it was confirmed that an amount of epoxy groups that completely reacted MCA disappeared.
< Synthesis example 7 >
jER-828 23.0g, CA 20.0g, and BTEAC 0.31g were dissolved in PM 101.0g, and reacted at 120 ℃ for 20 hours to obtain a photo-alignment compound (solid content concentration: 30 mass%) (PA 7). The epoxy value of the obtained compound was measured, and it was confirmed that the epoxy group in an amount that all CA was reacted had disappeared.
< Synthesis example 8 >
TEPIC-L13.4 g, CA 20.0g, and BTEAC 0.31g were dissolved in PM 78.6g, and reacted at 120 ℃ for 20 hours to obtain a photo-alignment compound (solid content concentration 30 mass%) (PA 8). The epoxy value of the obtained compound was measured, and it was confirmed that the epoxy group in an amount that all CA was reacted had disappeared.
Synthesis of component (B)
Synthesis example 9
25.0g of BMAA and 1.04g of AIBN as a polymerization catalyst were dissolved in 48.4g of PM and reacted at 85 ℃ for 20 hours to obtain an acrylic copolymer solution (solid content concentration: 35% by mass) (PB 1). The obtained acrylic copolymer had Mn of 4,800 and Mw of 3,100.
Synthesis of component (C)
Synthesis example 10
MMA (100.0 g), HEMA (11.1 g), and a polymerization catalyst (5.6 g) were dissolved in PM (450.0 g) as AIBN, and reacted at 80 ℃ for 20 hours to obtain an acrylic copolymer solution (solid content concentration: 20 mass%) (PC 1). The obtained acrylic copolymer had Mn of 4,200 and Mw of 7,600.
< examples, comparative examples >
The compositions for forming a cured film of each of the examples and comparative examples were prepared in the compositions shown in Table 1. Next, cured films were formed using the respective compositions for forming a retardation material, and the alignment properties were evaluated for all of the obtained cured films.
TABLE 1
Figure BDA0001405366870000461
[ evaluation of orientation ]
< examples 1 to 7, 16 >
Each of the cured-film-forming compositions of examples 1 to 7 and comparative example 2 was coated on a TAC film using a bar coater so that the wet film thickness was 4 μm. Then, they were dried by heating in a thermal circulation oven at 110 ℃ for 60 seconds to form respective cured films on the substrates. To each cured film at a rate of 5mJ/cm 2 Or 20mJ/cm 2 The alignment material was formed by vertically irradiating 313nm of linearly polarized light with the exposure value of (1). The polymerizable liquid crystal solution for horizontal alignment was applied to the alignment material on the substrate by a bar coater, and then prebaked on a 70 ℃ hot plate for 60 seconds to form a coating film having a thickness of 1.0. Mu.m. Coating film on the substrate at 300mJ/cm 2 And exposing to prepare the phase difference material. The retardation material on the produced substrate was sandwiched between a pair of polarizing plates, and the state of the retardation property of the retardation material was observed, and in the column of "orientation", the case where the retardation was not expressed as a defect was described as "O", and the case where the retardation was not expressed as "X". The evaluation results are summarized in table 2 below.
< examples 8 to 15, 17 to 18, and comparative example 1 >
Each of the cured-film-forming compositions of examples 8 to 15, 17 to 18 and comparative example 1 was applied to alkali-free glass using a spin coater so that the film thickness was 200nm. Then, they were dried by heating at 100 ℃ for 60 seconds on a hot plate, respectively, to form respective cured films on the substrates. The thickness of each cured film was 5mJ/cm 2 Or 20mJ/cm 2 Exposure of (2) vertically irradiating a 313nm straight lineLinearly polarizing the light to form an alignment material. A polymerizable liquid crystal solution for planar alignment was applied to the alignment material on the substrate using a spin coater, and then prebaked on a hot plate at 65 ℃ for 60 seconds to form a coating film having a thickness of 1.0. Mu.m. The coating film on the substrate was allowed to stand at 300mJ/cm 2 Exposing to produce the phase difference material. The retardation material on the produced substrate was sandwiched between a pair of polarizing plates, and the state of the retardation property of the retardation material was observed, and in the column of "orientation", the case where the retardation was not expressed as a defect was described as "O", and the case where the retardation was not expressed as "X". The evaluation results are summarized in table 2 below.
TABLE 2
Figure BDA0001405366870000481
Examples 1 to 15, which can be at 5mJ/cm 2 Such a low exposure amount forms a phase difference material. Examples 16 to 18 can be made at 20mJ/cm 2 The exposure amount of (a) forms a phase difference material. On the other hand, comparative example 1 did not obtain liquid crystal alignment properties.

Claims (7)

1. A cured film-forming composition comprising a compound as component (A), a crosslinking agent as component (B), and a crosslinking catalyst as component (D),
the compound as the component (A) is a reaction product of a cinnamic acid compound represented by the following formula (1) and a compound having 2 or more epoxy groups in one molecule,
Figure FDF0000019370940000011
in the formula, R 1 、R 2 、R 3 、R 4 And R 5 Each independently represents a hydrogen atom, a halogen atom, C 1 ～C 6 Alkyl radical, C 1 ～C 6 Haloalkyl, C 1 ～C 6 Alkoxy radical, C 1 ～C 6 Taking from haloalkoxy, cyano and nitro groupsA substituent group is replaced by a substituent group,
and, R 3 Are substituents other than the hydrogen atom in the above definition,
the crosslinking agent as the component (B) is: a polymer produced using an acrylamide compound or a methacrylamide compound substituted with a methylol group or an alkoxymethyl group, an alkoxymethylated glycoluril, an alkoxymethylated benzoguanamine or an alkoxymethylated melamine,
and the component (B) is 1 to 600 parts by mass based on 100 parts by mass of the component (A).
2. The composition for forming a cured film according to claim 1, further comprising a polymer having a thermally crosslinkable group as the component (C).
3. The composition for forming a cured film according to claim 2, wherein the component (C) is contained in an amount of 1 to 400 parts by mass based on 100 parts by mass of the total amount of the component (A) and the crosslinking agent as the component (B).
4. The composition for forming a cured film according to claim 1, wherein the component (D) is contained in an amount of 0.01 to 20 parts by mass based on 100 parts by mass of the total amount of the component (A) and the crosslinking agent as the component (B).
5. A cured film which is a cured product of the composition for forming a cured film according to any one of claims 1 to 4.
6. An alignment material which is a cured product of the composition for forming a cured film according to any one of claims 1 to 4.
7. A phase difference material comprising a cured film obtained from the composition for forming a cured film according to any one of claims 1 to 4.
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TWI773743B (en) * 2017-03-27 2022-08-11 日商日產化學工業股份有限公司 Cured film formation composition, orientation material and retardation material
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6156479A (en) * 1997-09-30 2000-12-05 Brewer Science, Inc. Thermosetting anti-refective coatings
US20010053437A1 (en) * 1997-11-28 2001-12-20 Kuniaki Sato Photo-cured film, and photosensitive element, printed wiring board and semiconductor package using such film
CN104204120A (en) * 2012-03-28 2014-12-10 日产化学工业株式会社 Composition for forming cured film, orientation material, and phase difference material

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS55165858A (en) 1979-06-13 1980-12-24 Toppan Printing Co Ltd Center-bound bookbinding folding pagination and its processing method
EP0611786B1 (en) 1993-02-17 1999-04-14 Rolic AG Orientation layer for liquid crystals
US5512607A (en) * 1995-06-06 1996-04-30 W. R. Grace & Co.-Conn. Unsaturated epoxy ester with quaternary ammonium and phosphate groups
JP3767962B2 (en) 1997-02-19 2006-04-19 シャープ株式会社 Video display system
WO1999015576A1 (en) 1997-09-25 1999-04-01 Rolic Ag Photocrosslinkable polyimides
JP2005049865A (en) 2003-07-17 2005-02-24 Arisawa Mfg Co Ltd Manufacturing method of optical phase difference element
JP5316740B2 (en) 2007-08-30 2013-10-16 Ｊｓｒ株式会社 Method for forming liquid crystal alignment film
WO2013011677A1 (en) * 2011-07-19 2013-01-24 パナソニック株式会社 Resin composition, resin varnish, prepreg, metal-clad laminate, and printed wiring board
JP5828314B2 (en) * 2012-09-12 2015-12-02 Jsr株式会社 Liquid crystal alignment agent
KR102294744B1 (en) * 2012-10-24 2021-08-30 닛산 가가쿠 가부시키가이샤 Cured-film-forming composition, alignment material, and phase-difference material
US9529132B2 (en) * 2013-03-08 2016-12-27 Nissan Chemical Industries, Ltd. Cured film formation composition, orientation material, and retardation material
JP6250324B2 (en) * 2013-08-02 2017-12-20 大阪有機化学工業株式会社 Composition for photo-alignment film and novel polymer
US11674053B2 (en) * 2013-09-19 2023-06-13 Nissan Chemical Industries, Ltd. Composition for forming underlayer film of self-assembled film including aliphatic polycyclic structure

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6156479A (en) * 1997-09-30 2000-12-05 Brewer Science, Inc. Thermosetting anti-refective coatings
US20010053437A1 (en) * 1997-11-28 2001-12-20 Kuniaki Sato Photo-cured film, and photosensitive element, printed wiring board and semiconductor package using such film
CN104204120A (en) * 2012-03-28 2014-12-10 日产化学工业株式会社 Composition for forming cured film, orientation material, and phase difference material

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